EP0224292B1 - Verfahren zur Herstellung von organischen Isocyanaten - Google Patents
Verfahren zur Herstellung von organischen Isocyanaten Download PDFInfo
- Publication number
- EP0224292B1 EP0224292B1 EP86201944A EP86201944A EP0224292B1 EP 0224292 B1 EP0224292 B1 EP 0224292B1 EP 86201944 A EP86201944 A EP 86201944A EP 86201944 A EP86201944 A EP 86201944A EP 0224292 B1 EP0224292 B1 EP 0224292B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- palladium
- group
- carried out
- ligand
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 32
- 239000012948 isocyanate Substances 0.000 title claims description 12
- 150000002513 isocyanates Chemical class 0.000 title claims description 12
- 239000002253 acid Substances 0.000 claims description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- -1 aromatic nitro compound Chemical class 0.000 claims description 20
- 150000007513 acids Chemical class 0.000 claims description 16
- 239000003446 ligand Substances 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 150000002941 palladium compounds Chemical class 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- MRUDNSFOFOQZDA-UHFFFAOYSA-N 2,6-dichlorobenzoic acid Chemical compound OC(=O)C1=C(Cl)C=CC=C1Cl MRUDNSFOFOQZDA-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 150000002940 palladium Chemical class 0.000 claims description 4
- LEDKKDPOPIKMSZ-UHFFFAOYSA-N 2,4,5-trichlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(Cl)=C(Cl)C=C1Cl LEDKKDPOPIKMSZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 22
- 239000011541 reaction mixture Substances 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 5
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 5
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- GLBZQZXDUTUCGK-UHFFFAOYSA-N 1-nitro-4-[(4-nitrophenyl)methyl]benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1CC1=CC=C([N+]([O-])=O)C=C1 GLBZQZXDUTUCGK-UHFFFAOYSA-N 0.000 description 2
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 2
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 2
- XTRDKALNCIHHNI-UHFFFAOYSA-N 2,6-dinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O XTRDKALNCIHHNI-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- AGQSHPFFJUBBHR-UHFFFAOYSA-N 1,10-phenanthroline-5-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC3=CC=CN=C3C2=N1 AGQSHPFFJUBBHR-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- GHVMJSHEGZYRQL-UHFFFAOYSA-N 2,4,6-tribromobenzoic acid Chemical compound OC(=O)C1=C(Br)C=C(Br)C=C1Br GHVMJSHEGZYRQL-UHFFFAOYSA-N 0.000 description 1
- SJDXJURIQGALGO-UHFFFAOYSA-N 2,4,6-trichlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C(Cl)C=C(Cl)C=C1Cl SJDXJURIQGALGO-UHFFFAOYSA-N 0.000 description 1
- RAFFVQBMVYYTQS-UHFFFAOYSA-N 2,4,6-trichlorobenzoic acid Chemical compound OC(=O)C1=C(Cl)C=C(Cl)C=C1Cl RAFFVQBMVYYTQS-UHFFFAOYSA-N 0.000 description 1
- SJZATRRXUILGHH-UHFFFAOYSA-N 2,4,6-trifluorobenzoic acid Chemical compound OC(=O)C1=C(F)C=C(F)C=C1F SJZATRRXUILGHH-UHFFFAOYSA-N 0.000 description 1
- QQFWMPUXPLBWTG-UHFFFAOYSA-N 2,4,6-trifluorophenol Chemical compound OC1=C(F)C=C(F)C=C1F QQFWMPUXPLBWTG-UHFFFAOYSA-N 0.000 description 1
- CVJVWHJVNYJTKA-UHFFFAOYSA-N 2,6-dichlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C(Cl)C=CC=C1Cl CVJVWHJVNYJTKA-UHFFFAOYSA-N 0.000 description 1
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 description 1
- HHSDIWAVOYCKAW-UHFFFAOYSA-N 2,6-difluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C(F)C=CC=C1F HHSDIWAVOYCKAW-UHFFFAOYSA-N 0.000 description 1
- CKKOVFGIBXCEIJ-UHFFFAOYSA-N 2,6-difluorophenol Chemical compound OC1=C(F)C=CC=C1F CKKOVFGIBXCEIJ-UHFFFAOYSA-N 0.000 description 1
- DNKGIDURJINUOA-UHFFFAOYSA-N 2,9-dichloro-1,10-phenanthroline Chemical compound C1=C(Cl)N=C2C3=NC(Cl)=CC=C3C=CC2=C1 DNKGIDURJINUOA-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- ZDULHUHNYHJYKA-UHFFFAOYSA-N 2-propan-2-ylsulfonylpropane Chemical compound CC(C)S(=O)(=O)C(C)C ZDULHUHNYHJYKA-UHFFFAOYSA-N 0.000 description 1
- YNFBMDWHEHETJW-UHFFFAOYSA-N 2-pyridin-2-yl-1h-benzimidazole Chemical compound N1=CC=CC=C1C1=NC2=CC=CC=C2N1 YNFBMDWHEHETJW-UHFFFAOYSA-N 0.000 description 1
- WPTCSQBWLUUYDV-UHFFFAOYSA-N 2-quinolin-2-ylquinoline Chemical group C1=CC=CC2=NC(C3=NC4=CC=CC=C4C=C3)=CC=C21 WPTCSQBWLUUYDV-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 1
- JIVLDFFWTQYGSR-UHFFFAOYSA-N 4,7-dimethyl-[1,10]phenanthroline Chemical compound C1=CC2=C(C)C=CN=C2C2=C1C(C)=CC=N2 JIVLDFFWTQYGSR-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- HZZQDMGIGCTARB-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline-2,3-disulfonic acid Chemical class C=1C=CC=CC=1C1=C(S(O)(=O)=O)C(S(=O)(=O)O)=NC(C2=NC=C3)=C1C=CC2=C3C1=CC=CC=C1 HZZQDMGIGCTARB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UBSRTSGCWBPLQF-UHFFFAOYSA-N 4-chloro-2-(4-chloropyridin-2-yl)pyridine Chemical group ClC1=CC=NC(C=2N=CC=C(Cl)C=2)=C1 UBSRTSGCWBPLQF-UHFFFAOYSA-N 0.000 description 1
- IMEVSAIFJKKDAP-UHFFFAOYSA-N 4-methoxy-2-(4-methoxypyridin-2-yl)pyridine Chemical group COC1=CC=NC(C=2N=CC=C(OC)C=2)=C1 IMEVSAIFJKKDAP-UHFFFAOYSA-N 0.000 description 1
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical group CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- OTMYLOBWDNFTLO-UHFFFAOYSA-N 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine Chemical compound C1=CC=CC=C1C1=NN=C(C=2N=CC=CC=2)N=C1C1=CC=CC=C1 OTMYLOBWDNFTLO-UHFFFAOYSA-N 0.000 description 1
- XDUUQOQFSWSZSM-UHFFFAOYSA-N 5-chloro-1,10-phenanthroline Chemical compound C1=CC=C2C(Cl)=CC3=CC=CN=C3C2=N1 XDUUQOQFSWSZSM-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004072 SiFe Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 150000005182 dinitrobenzenes Chemical class 0.000 description 1
- VMMLSJNPNVTYMN-UHFFFAOYSA-N dinitromethylbenzene Chemical class [O-][N+](=O)C([N+]([O-])=O)C1=CC=CC=C1 VMMLSJNPNVTYMN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- ZVSLRJWQDNRUDU-UHFFFAOYSA-L palladium(2+);propanoate Chemical compound [Pd+2].CCC([O-])=O.CCC([O-])=O ZVSLRJWQDNRUDU-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/14—Preparation of derivatives of isocyanic acid by catalytic reaction of nitro compounds with carbon monoxide
Definitions
- the invention relates to a process for the preparation of organic isocyanates by reacting an aromatic nitro compound with carbon monoxide in the presence of a catalytic system based on palladium and/or a palladium compound and a group 5A ligand.
- Organic isocyanates are valuable and versatile starting materials, for example for the production of polyurethanes and related compounds.
- organic isocyanates are prepared by contacting an aromatic nitro compound with carbon monoxide in the presence of a catalyst system comprising a platinum group metal compound, an aromatic nitrogenous heterocyclic compound and a component selected from water, hydrogen, hydrogen halides, boric acids, formic acid, oxalic acid and formaldehyde.
- a catalyst system comprising a platinum group metal compound, an aromatic nitrogenous heterocyclic compound and a component selected from water, hydrogen, hydrogen halides, boric acids, formic acid, oxalic acid and formaldehyde.
- organic isocyanates can be produced at a relatively low pressure, with a high reaction rate and with high selectivity when the process described in the beginning of this specification is carried out in the presence of a distinct type of ligand and of an acid.
- This favourable effect of the addition of an acid only occurs when the reaction is carried out with the distinct type of ligand used according to the invention, and not with ligands such as, for example, triphenylphosphine or pyridine.
- the present invention provides a process for the preparation of organic isocyanates by reacting an aromatic nitro compound with carbon monoxide, which process is carried out in the presence of a catalytic system prepared by combining:-
- the process according to the present invention is not only advantageous in that the aromatic nitro compound can be converted into the appropriate isocyanate with selectivities above 90%, but also because corrosion problems are of little significance. Furthermore, the recovery of palladium is not very cumbersome. Another important feature of the process of the invention is that it enables the preparation of isocyanates from aromatic nitro compounds and CO under moderate conditions in good yield and with a high reaction rate. In view of this the process is of great practical interest.
- the bridging groups X and Y in formula are connected with each other via the two carbon atoms shown in the formula. Apart from the connection as shown there may exist a second connection between the bridging groups, as is the case in 1,10-phenanthroline and derivatives thereof. Any atoms in the bridging groups X and Y other than carbon atoms are preferably nitrogen atoms. Furthermore, X and Y are preferably the same.
- Suitable bidentate ligands of formula I are 2,2'-bipyridyl and derivatives thereof, for example 4,4'-dimethyl-2,2'-bipyridyl, 4,4'-dichlorobipyridyl, 4,4'-dimethoxybipyridyl, 4,4'-dicarboxybipy- ridyl and 2,2'-biquinolyl.
- bidentate ligands of formula I are 1,10-phenanthroline and derivatives thereof, for example 5-chlorophenanthroline, 4,7-diphenylphenanthroline, 4,7-dimethylphenanthroline, 2,9-dichlorophenanthroline, 1,10-phenanthroline-5-sulphonic acid and the 4,7-diphenyl-1,10-phenanthroline-disulphonic acids.
- bidentate ligands of formula I are 2-(2-pyridyl)benzimidazole, 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine and the monosodium salt of 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine- p,p'-disulphonic acid.
- the bidentate ligand preferably present in the catalytic system is 2,2'-bipyridyl or a derivative thereof or 1,10-phenanthroline or a derivative thereof. Particularly preferred are 2,2'-bipyridyl and 1,10-phenanthroline..
- R represents an optionally substituted aromatic group
- Q represents an SOsH, OH or C(O)OH group.
- the aromatic group represented by R may be, for example, a 1-naphthyl, 2-naphthyl, 1-,2-or 9-anthryl, 4-phenanthryl, or, what is preferred, an optionally substituted phenyl group.
- the aromatic group may be substituted with, for example, alkyl, cycloalkyl, phenyl, alkoxy, cycloalkoxy, phenoxy and, what is preferred, halogen atoms, i.e.
- Preferred acids are 2,4,5-trichlorobenzenesulphonic acid, pentachlorophenol, 2,6-dichlorobenzoic acid and p-toluenesulphonic acid.
- acids of formula II are benzenesulphonic acid, 2,6-dichlorobenzenesulphonic acid, 2,6-dibro- mobenzenesulphonic acid, 2,6-difluorobenzenesulphonic acid, 2,4,6-trichlorobenzene sulphonic acid, 2,6-dichlorophenol, 2,6-difluorophenol, 2,4,6-tribromophenol, 2,4,6-trifluorophenol, 2,4,6-trichlo- robenzoic acid, 2,4,6-tribromobenzoic acid and 2,4,6-trifluorobenzoic acid.
- the acid of the general formula II may be an ion exchange resin containing sulphonic acid groups, such as, for example, Amberlite 252H ("Amberlite” is a trade name), the group R being a polymeric hydrocarbon group, for example a polystyrene group substituted with sulphonic acid groups.
- Amberlite 252H Amberlite 252H
- the group R being a polymeric hydrocarbon group, for example a polystyrene group substituted with sulphonic acid groups.
- Use may be made of two or more different protonic acids of the general formula II, for example of an acid of formula II in which Q represents an S0 3 H group and one in which Q represents an OH group or a C(O)OH group, or of an acid of formula II in which Q represents an OH group and one in which Q represents a C(O)OH group.
- protonic acids that may be used in the process according to the present invention are those that can be formed, possibly in situ, by interaction of a Lewis acid, such as, for example, BF s , AsFs, SbFs, PFs, TaFs or NbFs with a Broensted acid such as, for example, a hydrohalogenic acid, in particular HF, fluorosulphonic acid, phoshoric acid or sulphuric acid.
- a Lewis acid such as, for example, BF s , AsFs, SbFs, PFs, TaFs or NbFs
- a Broensted acid such as, for example, a hydrohalogenic acid, in particular HF, fluorosulphonic acid, phoshoric acid or sulphuric acid.
- a hydrohalogenic acid in particular HF, fluorosulphonic acid, phoshoric acid or sulphuric acid.
- sulphonic acids that can be used are fluorosulphonic acid, trifluoromethyl
- protonic acids are alkanoic acids, particularly those having not more than 12 carbon atoms per molecule, for example acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, heptanoic acid and lauric acid.
- n protonic acids n being an integer, for example 2, not more than n-1 protonic acids may be present in the form of salts thereof with a transition metal, for example with copper, iron, cobalt, nickel, manganese, chromium, vanadium or titanium.
- a salt of a transition metal particularly copper, of an acid of formula II in which R represents an optionally substituted phenyl group and Q an SOaH group, in combination with an acid of formula II in which R also represents an optionally substituted phenyl group and Q a C(O)OH group.
- the process according to the present invention is carried out in the presence of palladium and or a palladium compound.
- Palladium can be used as such, deposited on an inert carrier such as carbon or alumina, or in the form of palladium compounds, especially palladium salts. Good results can also be obtained when a palladium compound is used which is substantially soluble in the prevailing reaction mixture.
- Examples of convenient palladium salts include palladium chloride, palladium bromide, palladium iodide, sodium tetrachloropalladate, potassium tetrachloropalladate, potassium tetra-iodopalladate, palladium acetate, palladium propionate, palladium isobutyrate, palladium acetylacetonate and similar palladium compounds.
- the isocyanates are prepared from aromatic nitro compounds, i.e. compounds containing at least one aromatic group in which an N0 2 group is directly attached to a carbon atom forming part of an aromatic nucleus.
- aromatic nitro compounds include nitrobenzene, alkyl- and alkoxy-nitrobenzenes, aryl- and aryloxy-nitrobenzenes, dinitrobenzenes, alkyl- and alkoxy-, aryl- and aryloxy-dinitrobenzenes, such as 2,4-dinitrotoluene, 2,6-dinitrotoluene and 4,4 ' -dinitrodiphe- nylmethane, and polynitrobenzenes.
- Preferred aromatic nitro compounds are nitrobenzene, m-dinitrobenzene, 2-, 3- and 4-nitrotoluene, 2,4-dinitrotoluene, 2,6-dinitrotoluene and 4,4'-dinitrodiphenyl- methane. Mixtures of two or more aromatic nitro compounds can be applied, e.g. a mixture of two dinitro- toluenes.
- the amount of palladium or palladium compound to be used in the process according to the present invention is conveniently between 0.001 %w and 10 %w, in particular between 0.005 %w and 3 %w, calculated on the amount of nitro compound present in the reaction mixture.
- the ligands according to the general formula I may be used in such an amount that the ratio (palladium or palladium compound): ligand according to the general formula I is conveniently between 0.05 and 50, preferably between 0.1 and 20.
- the amount of protonic acid present in the reaction mixture preferably lies between 0.01 and 150, more preferably between 0.1 and 100, and most preferably between 1 and 50 equivalents per gram atom of palladium.
- a molar ratio ligand of formula I to protonic acid in the range of from 0.2 to 5 is suitably used.
- the process according to the present invention can be carried out conveniently at temperatures up to 300 ° C. Preference is given to the use of temperatures in the range between 75 ° C and 200 ° C, in particular between 85 ° C and 175 °C.
- the reaction is normally carried out at superatmospheric pressure; pressures of up to 500 bar can be applied. Preferably, the process is operated at a pressure in the range of from 10 to 150 bar. Good results can already be obtained using initial pressures between 30 and 80 bar.
- aprotic solvent examples include hydrocarbons such as hexane, cyclohexane, octane, benzene, toluene, the threee xylenes, ethylbenzene and cumene; halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, perfluoroalkanes, chlorobenzene and the three dichlorobenzenes; ethers such as tetrahydrofuran, diethyl ether, 3,6-dioxaoctane, methyl tert.-butyl ether, dioxane, anisole, 2,5,8-trioxanonane (also referred to as "diglyme”) diphenyl ether and diisopropyl ether; N,N-dialkyl-substituted amides, such as N,N-diofurane, diethyl ether, 3,6-dioxa
- the process according to the present invention can be carried out batchwise, semi-continuously or continuously.
- the reaction time is, of course, related to the temperature and pressure adopted. In general, reaction times between 1 and 20 hours appear to be adequate.
- Hastelloy C autoclave (“Hastelloy” is a trade mark).
- the selectivity to a certain compound, expressed in a percentage, is defined herein as 100 x a/b, in which "a” is the amount of starting compound that has been converted into that certain compound and "b” is the total amount of starting compound that has been converted.
- Example 1 was carried out as follows. The autoclave was charged with nitrobenzene (7.5 ml), toluene (50 ml), palladium(II) acetate (0.8 mmol), 2,2'-bipyridyl (10 mmol), p-toluenesulphonic acid (1 mmol) and pentachlorophenol (5 mmol). Then, consecutively, the autoclave was pressurized with carbon monoxide until an initial pressure of 70 bar was reached, the temperature was raised to 150 ° C, the reaction mixture was kept at this temperature for 5h, the reaction mixture was allowed to cool to ambient temperature and was analysed using gas-liquid chromatography.
- Examples 2-7 were carried out in the same manner as Example 1, but with the differences as stated in Table 1; the results of Examples 4-7 were measured after 3 h. This table also presents the results.
- the autoclave was charged with nitrobenzene (7.5 ml), diglyme (50 ml), palladium (II) acetate (0.8 mmol), 2,2'-bipyridyl (20 mmol), p-toluenesulphonic acid (1 mmol) and acetic acid (20 mmol). Then, consecutively, the autoclave was pressurized with carbon monoxide (initial pressure 60 bar), the temperature was raised to 150 ° C, the reaction mixture was kept at this temperature for 1.5 h and the reaction mixture was allowed to cool to ambient temperature. The conversion of nitrobenzene was 80%, with a selectivity to phenyl isocyanate of 61%.
- the autoclave was charged with nitrobenzene (15 ml), diglyme (42.5 ml), palladium (II) acetate (0.8 mmol), 2,2'-bipyridyl (20 mmol), cupric tosylate (1 mmol) and 2,6-dichlorobenzoic acid (10 mmol). Then, consecutively, the autoclave was pressurized with carbon monoxide (inital pressure 70 bar), the temperature was raised to 150 ° C, the reaction mixture was kept at this temperature for 5 h and the reaction mixture was allowed to cool to ambient temperature. The conversion of nitrobenzene was 40%, with a selectivity to phenyl isocyanate of 85%.
- the autoclave was charged with nitrobenzene (15 ml), p-xylene (50 ml), palladium(II) acetate (0.8 mmol), 1,10-phenanthroline (10 mmol), 2,4,5-trichlorosulphonic acid (1 mmol) and 2,6-dichlorobenzoic acid (10 mmol). Then, consecutively, the autoclave was pressurized with carbon monoxide (initial pressure 70 bar), the temperature was raised to 150 ° C, the reaction mixture was kept at this temperature for 3 h and the reaction mixture was allowed to cool to ambient temperature. The conversion of nitrobenzene was 46%, with a selectivity to phenyl isocyanate of 60%.
- the autoclave was charged with nitrobenzene (7.5 ml), diglyme (50 ml), palladium(II) acetate (0.2 mmol), pyridine (20 mmol), p-toluenesulphonic acid (1 mmol) and acetic acid (20 mmol). Then, consecutively, the autoclave was pressurized with carbon monoxide (initial pressure 60 bar), the temperature was raised to 150 ° C, the reaction mixture was kept at this temperature for 5 h and the reaction mixture was allowed to cool to ambient temperature. Phenyl isocyanate could not be detected in the reaction mixture.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Claims (15)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB858528532A GB8528532D0 (en) | 1985-11-20 | 1985-11-20 | Preparation of organic isocyanates |
GB8528532 | 1985-11-20 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0224292A1 EP0224292A1 (de) | 1987-06-03 |
EP0224292B1 true EP0224292B1 (de) | 1990-04-11 |
Family
ID=10588481
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86201944A Expired - Lifetime EP0224292B1 (de) | 1985-11-20 | 1986-11-06 | Verfahren zur Herstellung von organischen Isocyanaten |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0224292B1 (de) |
JP (1) | JPH0796541B2 (de) |
CA (1) | CA1295338C (de) |
DE (1) | DE3670285D1 (de) |
ES (1) | ES2016255B3 (de) |
GB (1) | GB8528532D0 (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8601962D0 (en) * | 1986-01-28 | 1986-03-05 | Shell Int Research | Preparation of carbamates |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3576835A (en) * | 1967-12-18 | 1971-04-27 | Olin Corp | Preparation of aromatic isocyanates |
US3923850A (en) * | 1969-03-12 | 1975-12-02 | Olin Corp | Preparation of aromatic isocyanates |
DD105211A5 (de) * | 1972-03-07 | 1974-04-12 |
-
1985
- 1985-11-20 GB GB858528532A patent/GB8528532D0/en active Pending
-
1986
- 1986-11-03 CA CA000522036A patent/CA1295338C/en not_active Expired - Fee Related
- 1986-11-06 ES ES86201944T patent/ES2016255B3/es not_active Expired - Lifetime
- 1986-11-06 DE DE8686201944T patent/DE3670285D1/de not_active Expired - Fee Related
- 1986-11-06 EP EP86201944A patent/EP0224292B1/de not_active Expired - Lifetime
- 1986-11-18 JP JP61273089A patent/JPH0796541B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS62142148A (ja) | 1987-06-25 |
ES2016255B3 (es) | 1990-11-01 |
GB8528532D0 (en) | 1985-12-24 |
CA1295338C (en) | 1992-02-04 |
EP0224292A1 (de) | 1987-06-03 |
JPH0796541B2 (ja) | 1995-10-18 |
DE3670285D1 (de) | 1990-05-17 |
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